Quaternary ammonium derivatives of chloroxy propylated oxyalkylated phenol-aldehyde resins



Patented Jan. 8, 1952 'QUA'PERNARY DERIVATIVES or JGHLOROXY $3"PROPYIIATED .ci'ifoxYALKY-L- 4*; ."ATED fRHENOE-FALDEHYDE: RESINS- 1.iMelvifi D61fimotliUnivei-sitii:Cithahd Bernhard Keisei-i'webstefGroves, Mouassignors toBetrolitflorpofiatioii'yLtd, -WilmingtoxiiDelr,aicorporation of Delaware The present-invention is concernedwithcertainnew chemicalproducts compounds or com- -positions which have usefulapplication in'warious arts. These compoundsaw -quaternary ammoniumcompounds '-prepa-red" iri the wma-n-ner hereinafter described.

Our invention includes -meth'ods or :procedu-res *for manufacturings'aid 'new chemical-products, ----compounds, or compositions asetvellrasthe products, compounds, or compdsitionsthem selves. Said new compoundsor compositions are quaternary :ammonium *compounds derived by reactionbetween 'fill' achloro-oxypropylated derivative ofhydroph-ile"hydroxylated synthetic -.products; said hydrophile syntheticproducts 'being oxyalkylationproductsbf (A) An alpha-beta alkylene oxidehaving not more than 4 carbon 'atomsand selected from the classconsisting: ofcrethylenes-:-oxide,;;2propylene oxide;=butylenetoxide;'.:glycidezandi and (B)" An z,oxyalkylationesusceptibleimsiblewor- ,yganicsolvent-soluble; waters-'insolubl henolaldehyde resinsaid tresin-:beinaaderivednbyereaction between avdifunctionalimonoh'ydric. phe- 1 nol and.an;aldehydevhavingrmotnover.ltz carbon :atoms and reactive. -tow.ard.::said t'rnhenoly usaid resinbeing formed: :izrathe'" substantialnabsence of, trifunctionalphenolsxasaidr phenol being-50f the formula:

in which R is a hydrocarbon radical havingnt 'least 4 and not morethan"12 :carbon atoms and substituted in the 2,4,6positionssaid-oxyalkylated resin being characterizedbyzrthekintroductioninto the resin molecule of a plurality tof divalentradicals having theformula (R10). nfilill which Rlsis a member selected from theiiclas'sconsisting of ethylene radicals, propylene eradicals, butylene radicals,hydroxypropylene 'iadicals, and .ihydroxybutylene:radicals;.:and ngisxanumeral-varying from 1 156120; witli'fdzhe proviso that at least 2 molesof alkylene oxide be intro- ..duced foreach-phenolicnucleus isaidchlorooxypropylated compounds being obtained by -reaction withepichlorohydrin; and (2) a ibasic tertiary amine having not over'50c'arbon'atoms. ...-.-A1though the--:herein':'idescribed productsahave avnumber of industrial gapplicationsgrtheysareZof .;particular value forresolvingqietroleumeeeniul-' sions of the water=in oil'typetliatarecommonly l methylglyci'de 1 (Cl. zeosssz) 1?"!2 referred to as cut oil,"roily oil, emulsified -':oil,-: *etc.-,= and which comprise "finedroplets of naturally-occurring waters or' brines dispersed in a more or-less permanent state throughout 5 tnwmewnmnconstitutes the continuousphase ftcthe eniulsion. This specific application is escribed andclaimed in --our "co-pending appliati01i'-=Serla1 -No? 9l'j886j filed"May 6, 1949; now atent 2';542,0l1, -granted *February -20, 1 1951. Seealso our co-peiiding';application*Seria1 'No.

4i'469i-fll-ed December 10,-1-948.

whet-new products-"are'useful" as1 wetting, detergenteand leveling-agents,, in'-'th'er laundryy'texleahd' dyeing industries; "aswetting'agents "and "16 =detergents z-in the acid washing 'ofbuildingstone e aiid bricka as wetting agents and Spreaders in".rtheuapplication or asphaltdn' road building. and ..th e like;; 848 a'flotation"reagent in the; flotation egatively charged" particles'tsuchas ewagercoah washing -wasterwater, and various rade:=wastes '-andthelikey'awgermicides; inecticideaeniulsifying agents, as, :for:example, or-cosmeticsr spray"oilspwater-repellent textile M2 finishes;a's lubricantsfetc.

@The i-nstant"ammoniumwompounds are of articular value"'ffor 'variouspurposes [where uatemary. 'ammo'nium nomp'ounds'L. have? foundpcificaapplication.

, i heoxyalkylated resinsp us'ed as' intermediates toeproduce the*products "i'ofthis applica- Ion-ware described in *our Patents" '29199,37 0, grantei March 7 1950; and 2542,011; granted bruaryi20jl95l=randreferenceis made'toi these :rrsins used to produce thealcoholic products. PEor speific-rexamples ,of these resins, reference'sissmademo ltxamples 1a through 103a of Patent 212,499,370. Forexamples of oxyalkylated prod- .wgucts derived from these resins,reference is made ito'ithe tables in columns 31 throu h 46 of Patent"JIhe reaction ofiepichlorohydrin is, in essence, continuationof'thereaction involving ethylene 45 ICbiide, propylene soxidepror thelike. The same .requivalentzcan -beaused;;.but it is desirable to makeai'slight :c'hange inflthe matter of catalyst. The .-usual catalyst inthe "oxyalkylation of a material :when neither reactanta'containschloride, is an 50 .ialkali such as been pointed out previously.Howeveri eithervreacta'nt contains chlorine, another 2 -type ofireactantcanbe employed advantageously, tosvit on o'ii-themetallic chlorides suchas ferric chloride 1n'f"chlofide;-.etc. At times it is sub- "stantiallynecessary to use such a catalyst, for

the reason that if an alkali is used, it reacts with a labile chlorineand the catalyst is lost. Our preferred procedure then is to add aslight amount of para -to1uene sulfonic acid to the intermediateproducts so as to neutralize any residual alkalinity. We havethen addedsmall amounts of stannic chloride as a catalyst, so as to accelerate thereaction with epichlorohydrin.

The-* amount used is less than one-half of 1%, based j on the weight ofthe material, andusuallyone or two grams of stannic chloride aresufiicient in a reaction involving 300 to 600 grams of reactants. Due tothe higher boiling point of epichlorohydrin, as compared with ethyleneoxide,

for example, one can use identically the same equipment as employed inthe manufacture of resins, as described in Example 1a. of Patent2,499,370. In fact, it is our preference to use this particularequipment on a laboratory scale. 1

Example 10 The equipment employed was specifically that described inExample 16 of Patent 2,499,370. The resin solution employed was thatdescribed as 105D of Patent 2,542,011. instance, and in all subsequentexamples, just sufficient para-toluene sulfonic acid was added in eachcase, if required to bringthe product. to substantially a neutral state,i. e., neutral or very faintly acid to methyl orange indicator. 554grams of the oxyethylated resin solution were used, and to this therewas added 1.6 grams of stannic' chloride. The mixture was stirred. andheated to 95 C. The above amount represented .8 of a mole per phenolichydroxyl, based on the original phenol employed. The amount ofepichlorohydrin added was just sufficient to react with all the phenolichydroxyls, to wit, .8 of a mole, or 73.6 grams. The epichlorohydrin wasadded drop-wise with stirring and all oi it a temperature of 130 C. wasreached. At this point some of the liquid started to;;refiux at about125 to 130 C., with a thermometer in the vapor reading 127 C. Noreactant passed into the condenser. This indicated that -theepichlorohydrin must have reacted completely at the end of this period,for the reason that it boilsat 117 C. The yield was 520 grams whichcontained approximately xylene. all istabulatedinthe table below.

Note that in this cosity perhaps a trifle, at the most, but definitelydoes reduce'water-solubility. Our preference in all instances was toobtain materials, which, after treatment, with epiehlorohydrin, showed-water-solubility at least equal to that described as desirable inconnection with the oxyalkylated resin prior to treatment withepichlorohydrin. Stated another way, such material should meet theemulsification test, using xylene, as previously described.

' V Example 20 The same procedure was followed as in Example 1c,preceding, except that the oxyalkylated resin solution employed was thatpreviously described under the leading 11% of Patent 2,542,011. Thereactants employed were as follows: 645 grams of the resin solution; 55grams of epichlorohydrin, and 1.2 grams of stannic 15 minutes.

chloride. The catalyst and the oxyalkylated resin solution were mixedtogether, as in Example 1c, and the epichlorohydrin added in a 10-minuteperiod without any temperature rise. The temperature was then raised to135 to 140 0.. As the temperature moved upward, there was a certainamount of refluxing which took place at 127 C. This reflux appeared foronly a short period of time, and then the temperature rose ratherrapidly to the predetermined point of 135 to 140 C. It was held at thistemperature for one hour. At the end of this time, the reaction wascomplete. The final yield was approximately 700 grams containing about20% xylene. 7 Example 3c The same procedure was followed as in Example1c, preceding, except that the resin solution employed was thatdescribed as 123?) of Patent 2,542,011. The amount of this resinsolution employed was 779 grams. The amount of catalyst employed was 1.2grams. The amount 'of epichlorohydrin employed was 55.2 grams.The'resin, plus the catalyst, was heated to about C. and then theepichlorohydrin added in The temperature remained at 110 to C. for ashort period of time and then was raised to 140 C. and stirred for 30minutes. The yield was about 850 grams, containing about 17% xylene.

The same procedure was followed in a number of similar products and thedata for this series Epichlo Solv. Pres Ex ox ai k Altount m rog a mgnOli gg g ig ff gield m 11151 esm o rams se rams rams r0 ,P r

Grams Temp. 0. hours Cent 1 Ex. No. of Patent 2,542,011.

1 In these experiments apparently some of the epichloroliydrin was lostthrough the condenser. The amount which combined is definitely less thanthe initial amount, in view of the lower final yield.

5 In this case an unoxyethylated resin was dissolved with enough addedxylene to give a solution containing 40% xylene and 60% solvent.

The ultimate product was diluted with enough additional xylene so thatthe final product contained 30% and 70% resin which had been treatedwith eplchlorohydrin.

The chloro-oxypropylated compounds previously described have beenprepared in pres-.- ence of a slight amount of solvent, such as xylene.This xylene usually was residual from the preparation of the ester andcarried through the oxyalkylation stage and into the final stage. Wehave found this purely as a matter of convenience, particularly sincesolvent may be present for subsequent use, i. e., demulsification, orfor the preparation of more complex derivatives. Needless to say, thesolvent can be removed. In other words, the solvent, such as'xylene, canbe distilled out and particularly employing a vacuum of about 20 to 40mm. of mercury or thereabouts, and a temperature of 130 Q.

As previously pointed out, having obtained compounds in which there is alabile chlorine atom present, such as those described above, suchproducts are then used as intermediates for further reaction withtertiary amines, particularly basic tertiary amines, to producequaternary ammonium compounds. We have employed a large number oftertiary amines. In numerous cases these tertiary amines can bepurchased in the open market. In other instances they can be preparedfrom primary or secondary amines by procedures which convert such aminesinto tertiary amines, for example, treatment with a methylating agent,such as dimethylsulfate, or an alkylene oxide, such as ethylene oxide,propylene oxide, styrene oxide, etc.

The alkylamines are best prepared from higher fatty acid amines, such asthe primary fatty acid amines and secondary fatty amines listed inArmeen Price List No. 10, dated August 30, 1948, issued by Armour 8:Company, Chicago, Illinois. Rosin amines can be employed and areobtainable from Hercules Powder Company, Wilmington, Delaware. In ageneral way, the upper carbon atom limit in such amines is approximately50, as, for example, a dialkyl fatty amine obtained from fatty acidshaving 22 carbon atoms, which is then treated with dimethylsulfate,styrene oxide, etc., or treated with ethylene oxide or propylene oxide,particularly repetitiously. One example of such amine would bedi-octadecylamine, which was subsequently treated with 2 to 4 moles ofpropylene oxide.

Other suitable amines are the ester type, such as triethanolamine ortriethanolamine which has been treated with 3 moles of ethylene oxide.followed by esterification with a higher fatty acid. Similar basicesters are obtainable from tertiary amines, such as diethylethanolamine.For instance, We have employde diethylethanolamine stearate as preparedby Carbide 8: Carbon Chemicals Corporation, New York city, N. Y., anddesignated for trade purposes as Amine ES.

One is not limited to monoamines but polyamines also can be employed. Inthe treatment of polyamines one can add enough of the chlorinecontainingreactant to combine with one or more of the basic nitrogen atomspresent. Purely by way of examples, the following reactants aresuggested.

R=alkyl or alkanol. R1=a1kyl from R100, the acyl radical of a higherfatty acid, or the like.

The following examples and the table illustrate specific preparations:

Example 1d 65 grams of the chlorinated derivative identified as Example1c were mixed with 21.3 grams of dimethyldodecylamine. The temperaturerose to 28 C. and then 33 C. The mixture was held. at this temperaturefor 20 minutes and then allowed to stand overnight. It was then heatedto 140 C. for 6 hours. At the end of this time the reaction wascomplete.

Example 2d The same chlorinated derivative was used as in Example 1d.The particular tertiary amine employed was benzyldimethylamine. Theamounts employed were 130 grams of the chlori; nated derivativeidentified as 10, and 27 grams of benzyldimethylamine. The maximumtemperature employed was 140 C. and the reaction mass was held at thistemperature for a period of 5 hours. The final product was particularlysoluble in water.

Example. 3d

The same procedure was employed as in the preceding examples and thesame chlorinated derivative employed. 65 gramsof the compound identifiedas Example 10 were mixed with 32 grams of octylphenoxyethoxyethyldimethylamine. The material was heated to to C. for approximately 3hours. The product obtained was comparatively clear and the reac-- tionappeared to go more rapidly than in Example 1d, preceding.

Example 4d The procedure of the preceding example was employed and alsothe same chlorinated reactant. 65 grams of the material identified as 10were mixed with 8 grams of pyridine. The mixture was heated at 110 to C.for approximately 5 hours. The reaction with pyridine takes place ratherrapidly, although the products do not seem to be quite as soluble as insome other instances, as hereinafter noted.

Example 503 The same procedure was followed as in Example 4d, preceding,except that the 8 grams of pyridine were replaced by 18.5 grams oftri-N- butylamine. The product was heated at 120 C. for 8 hours. At theend of this time a slight odor of butylamine persisted in the sample,in-, dicating that there was still a very small proportion of unreactedamine present. The above experiments and additional experiments aresummarized in the following table.

Ex Epichloro.- Amt. Amt. Time of Deriv. Used Tertiary Amine Used Used ggReaction Ex. No. Grams Grams so Hours 1c W 65 Dimethyldodecylamine 21. 3140 6 1c 1 130 Benzyldimethylamine 27. 140 1c 65 32. 0 110 3% 1c 65 8. 0120 5 1c 65 18. 5 120 8 146 26. 6 110 7 20 146 17. 0 100 1 2c 58 6. 0120 2 2c 58 Pyridine 39. 0 100 4 2c 58 Tri-N-butylamlne 9. 3 100 3% 3c142 Dodecyl dimethylamine. 21. 3 140 4% 31: 142 Benzyldimethylamine. 13.5 120 3 142 Alpha picoliue 9. 3 120 2 30 142 Opeedma 1 32. 1 100 6% 30142 Dietliylcyclohexylamine. l5. 5 100 5% 4: 1299-Octadecenyldimethylaminc 29. 5 100 8 40 129 Pyridine 7. 9 135 3 4c 129Benzyldimethylmnine... 13. 5 150 3 do 129 Dimethylaniiine 12. l 150 6 is129 Methyl morpholine 13. 8 130 1 5c 82 Pyridine 2. 4 130 5c 82 4. 7 1301 5c 82 11. 9 130 1 5c 82 27. 8 120 3% 5c 82 Dodecyldimethyiamiue 32. 0155 3% 6!: 95.8 Pyrid ne 2. 4 130 1% 6c 95.8 Pyridine. 4. 74 135 1 6c95. 8 Pyridine. 23. 7 130 1% 6c 95. 8 Opeedma 38. 4 110 2% 6c 95. 8Dimcthyl Aniline 15. 5 150 6% 7c 129 Pyridine 7. 9 130 4 108. 5 Pyridinel l 4. 9 145 1 8c 108. 5 Benzyldimethylamine. 8. 4 135 1% 8c 1118. 5Tri-N-butylamine 11. 6 120 3% 80 108. 5 N methyl Morpholine. 9. 8 140 28c 91 Opeedma 1 l. 17. 7 140 5% 9:: 101 Pyridin I 8. 7 100 1 9a 101N-methyl Morpholin l1. 1 80 1 9a 101 4. 0 120 8% 101 35.0 140 1 10!: 1077. 9 130 5 10c 107 21. 0 130 7 10 107 85. 3 125 4 107 26. 9 100 2 10140. 0 130 3 110 101 9. 9 135, 2 110 101 19. 4 140 i 8% 11 101 12. 6 1405 lie 101 1. 6 140 3% 108 Opeedma 46. 0 140 5% 13 110 Opeedma es 4% 130110 Amine ES 76. 7 140 4% 140 116 Opeedma l v 96. 0 7 151: 118 N -methy1Morpholine 20. 2 120 3 V 1 Opeedma-OctylpheuoxyethoxyethylDimethylaminc.

such solvent can be eliminated in the customary 59 manner bydistillation, and particularly vacuum distillation, under approximately20 to 40 mm. of mercury at 130 to C. Our experience has been thatreaction of a tertiary amine generally gives the product a reddish tint;in other words, the final product is apt to be reddishblack, deep red,or reddish-amber. The viscosity of the final product is apt to begreater than the initial materials from which it is obtained,

and it is apt to be a solid, or a sticky or tacky solid. Theseproperties, of course, return to the product in absence of any solvent.We prefer, as a matter of convenience, to have enough solvent present orto add enough, so as to obtain a liquid material which can be handledeasily. By and large, we prefer that the original resin be treated withethylene oxide, rather than propylene oxide, or some other oxide, and wealso prefer that at least 5 moles of ethylene oxide be introduced foreach original phenolic nucleus. We have found that N-methyl morpholineand octylphenoxyethcxyethyl dimethylamine are particularly desirablereactants.

Pyridine and pyridine homologuesreact rapidly,

but our preference, when using these materials,

is to have at least 10 moles of ethylene oxide present per initialphenolic hydroxyl. As is noted, the products readily give water-solubleor water-dispersible compounds, for reasons which need not beenumerated, but particularly in light of the co-valency which appearsbetween the quaternary nitrogen compound or radical and the chlorineatom or ion.

Having thus described our invention, what we claim as new and desire tosecure by Letters Patent is:

1. A quaternary ammonium compound derived by reaction between (1) achloro-oxypropylat- 1 ed derivative-oi hydrophile hydroxylated syntheticproducts; said hydrophile synthetic products being oxyalkylationproducts of (A) an alpha-beta alkylene oxide having not more than 4carbon atoms and selected from the class consisting of ethylene oxide,propylene oxide, butylene oxide, glycide and methylglycide; and (B) anoxyalkylation-susceptible, fusible, organic solvent-soluble,water-insoluble, phenol-aldehyde resin; said resin being derived byreaction between a diiunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and having one functional group reactive towardsaid phenol; said resin being formed in the substantial absence ofphenols of functionin which R is a hydrocarbon radicalhaving at least 4and not more than 12 carbon atoms and substituted in one of thepositions ortho and para; said oxyalkylated resin being characterized bythe introduction into the resin'molecule at the phenolic hydroxyls of apluralityof divalent radicals having the formula (R1O)n, in which R1 isa member selected from the class consisting of ethylene radicals,propylene radi cals, butylene radicals, hydroxypropylene radicals, andhydroxybutylene radicals, and n is a numeral varying from 1 to 20; withthe proviso that at least 2 moles of alkylene oxide be introduced foreach phenolic nucleus; said chlorooxypropylated compounds being obtainedby reaction with epichlorohydrin; and (2) a basic tertiary amine havingnot over 50- carbon atoms.

2. A quaternary ammonium compound derived by reaction between (1) achloro-oxypropylated derivative of hydrophile hydroxylated syntheticproducts; said hydrophile synthetic products being oxyalkylationproducts of (A) an alpha-beta alkylene oxide having not more than 4carbon atoms and selected from the class consisting of ethylene oxide,propylene oxide, butylene oxide, glycide, and methylglycide; and (B) anoxyalkylation susceptible, fusible, organic solventsoluble,water-insoluble, phenol-aldehyde resin;

said resin bein derived by reaction between a difunctional monohydricphenol and an aldehyde having not over 8 carbon atoms and having onefunctional group reactive toward said phenol; said resin being formed inthe substantial absence of phenols of functionality greater than 2; saidphenol being of the formula:

in which R is a hydrocarbon radical having at least 4 and not more than12 carbon atoms and substituted in one of the positions ortho and para;said oxyalkylated resin being characterized by the introduction into theresin molecule at the phenolic hydroxyls of a plurality of divalentradicals having the formula (R) n, in which R1 is a member selected fromthe class consisting of ethylene radicals, propylene radicals, butyleneradicals, hydroxypropylene radicals, and hydroxybutylene radicals, and nis a numeral varying from 1 to with the proviso that at least 2,functional group reactive toward said phenol;

said resin being formed in the substantial absence of phenols offunctionality greater than 2; said phenol being of the formula:

in which R is a hydrocarbonradical having at least 4 and not'more than12 carbon atoms and substituted in one of the positions ortho and para;said oxylakylated resin being characterized by the introduction into theresin molecule at the phenolic hydroxyls of a plurality of divalentradicals having the formula (C2H40)n, and n is a numeral varying from 1to 20; with the proviso that at least 2 moles of ethylene oxide beintroduced for eaciz phenolic nucleus; said chloro-oxypropylatedcompounds being obtained by reaction with epichlorohydrin; and with thefurther proviso that the hydrophile properties of thechloro-oxypropylated derivative, as well as the oxyethylated resin, inan equal weight of xylene are sufficient to produce an emulsion whensaid xylene solution is shaken vigorously with one to three volumes ofwater; and (2) a basic tertiary monoamine having not over 50 carbonatoms.

4. A quaternary ammonium compound derived by reaction between (1) achloro-oxypropylated derivative of hydrophide hydroxylated syntheticproducts; said hydrophile synthetic products being oxyethylationproducts of an oxyethylatiom susceptible, fusible, organicsolvent-soluble water-insoluble; phenol-aldehyde resin; said resin beingderived by reaction between a difunctional monohydric phenol andformaldehyde; said resin being formed in the substantial absence ofphenols of functionality greater than 2; said phenol being of theformula:

in which R is a hydrocarbon radical having at least 4 and not more than12 carbon atoms and substituted in one of the positions ortho and para;said oxyalkylated resin being characterized by the introduction into theresin molecule at the phenolic hydroxyls of a plurality of divalentradicals having the formula (C2H4O)n; and n is a numeral varying from 1to 20; with the proviso that more than 4 moles of ethylene oxide beintroduced for each phenolic nucleus; said chloro-oxypropylatedcompounds being obtained by reaction with epichlorohydrin on theequimolar basis of one mole of the epoxy compound for each phenolichydroxyl originally present; and with the further proviso that thehydrophile properties of the chloro-oxypropylated derivative, as well asthe oxyethylated resin, in an equal weight of xylene are sufiicient tothe produce an emulsion when said xylene solution is shaken vigorouslywith one to three volumes of water; and (2) a basic tertiary monoaminehaving not over 50 carbon atoms.

5. The product of claim 4, wherein the amine is acyclic.

6. The product of claim 4, wherein the amine is aliphatic and has lessthan 30 carbon atoms.

7. The product of claim 4, wherein the amine is aliphatic and has lessthan 30 carbon atoms. and R is substituted in the para position.

8. The product of claim 4, wherein the amine is aliphatic and. has lessthan 30 carbon atoms, and R is a butyl radical substituted in the paraposition. v

9. The product of claim 4, wherein the amine is aliphatic and has lessthan 30 carbon atoms, and R is an amyl radical substituted in the paraposition.

10. The product of claim 4, wherein the amine is aliphatic and has lessthan 30 carbon atoms,

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,076,624 De Groote Apr. 13, 19372,499,365

De Groote Mar. '7, 1950

1. A QUATERNARY AMMONIUM COMPOUND DERIVED BY REACTION BETWEEN (1) ACHLORO-OXYPROPYLATED DERIVATIVE OF HYDROPHILE HYDROXYLATED SYNTHETICPRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING OXYALKYLATIONPRODUCTS OF (A) AN ALPHA-BETA ALKYLEN OXIDE HAVING NOT MORE THAN 4CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OF ETHYYLENE OXIDE,PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE AND METHYGLYCIDE; AND (B) ANOXYALKYLATION - SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENT-SOLUBLE,WATER-INSOLUBLE, PHENOL-ALDEHYDE RESIN; SAID RESIN BEING DERIVED BYREACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVINGNOT OVER 8 CARBON ATOMS AND HAVING ONE FUNCTIONAL GROUP REACTIVE TOWARDSAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OFPHENOLS OF FUNCTIONALITY GREATER THAN 2; SAID PHENOL BEING OF THEFORMULA: